Insecticidal and acaricidal phosphorous-containing esters of 2-hydroxyquinoxaline

ABSTRACT

Phosphoric, thionophosphoric, phosphonic, and thionophosphonic acid esters of 2-hydroxyquinoxaline of the formula   IN WHICH R is alkyl, R&#39;&#39; is alkyl, alkoxy or phenyl (said alkyl and alkoxy having 1 to 4 carbon atoms), and X is oxygen or sulfur, possess pesticidal, especially insecticidal and acaridical, properties.

United States Patent Schmidt et al.

[451 Apr. 29,1975

INSECTICIDAL AND ACARICIDAL PHOSPHOROUS-CONTAINING ESTERS OF Z-HYDROXYQUINOXALINE Inventors: Karl-Julius Schmidt,

Wuppertal-Vohwinkel; Ingeborg Hammann, Cologne, Germany Assignee: Bayer Akti'e'ngesellschaft,

Leverkusen. Germany Filed: Mar. 27, 1973 Appl. No.: 345,401

Related U.S. Application Data Division of Ser. No. 55l.553, May 20. 1966, Pat. No. 3.763.160.

3,172,888 3/1965 Miller et al. 260/250 3,216,894 I 1/1965 Lorenz et al 260/250 3,340,262 9/1967 Gagliardi et al. 260/250 3,763,160 l0/l973 Schmidt et al. 260/250 R Primary ExaminerAlbert T. Meyers Assistant E.\-aminerLeonard Schenkman Attorney, Agent, or Firm-Burgess, Dinklage & Sprung [57] ABSTRACT Phosphoric, thionophosphoric, phosphonic, and thionophosphonic acid esters of 2-hydroxyquinoxaline of the formula in which R is alkyl, R is alkyl. alkoxy or phenyl (said alkyl and alkoxy having 1 to 4 carbon atoms), and X is oxygen or sulfur, possess pesticidal, especially insecticidal and acaridical, properties.

11 Claims, No Drawings INSECTICIDAL AND ACARICIDAL PHOSPHOROUS-CONTAINING ESTERS OF Z-HYDROXYQUINOXALINE This is a division of application Ser. No. 551,553 filed May 20, 1966, now US, Pat. No. 3,763,160.

The present invention relates to particular new phosphorus-containing esters of Z-hydroxyquinoxaline, which have pesticidal, and especially insecticidal and acaricidal, properties, to their pesticidal compositions with dispersible carrier vehicles, and to methods for the preparation and use thereof.

Open chain and cyclic quinoxaline-2,3-thiophosphoric acid esters are already known from German Pat. No. 1,1 15,738. These products are obtained by reacting the corresponding 2,3-dimercaptoquinoxalines with alkylor aryl-phosphoric or -thionophosphoric acid monoester dihalides or diester monohalides.

According to said German patent, the compounds in question are characterized by a good insecticidal and acaricidal activity; they have an especially strong action against resistant spider mites. However, the production of this group of active compounds is comparatively difficult, at least on an industrial scale.

It is an object of the present invention to provide particular new phosphorus-containing esters, such as phosphoric, thionophosphoric, phosphonic, and thionophosphonic acid esters of Z-hydroxyquinoxaline, which possess valuable pesticidal, and especially insecticidal and acaricidal, activity; to provide active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles; to provide a process for producing such compounds; and to provide methods of using such compounds in a new way, especially for combating pests, such as insects and acarida, and the like.

Other and further objects of the present invention will become apparent from a study of the within specification and accompanying examples.

It has now been found, in accordance with the present invention, that phosphoric, thionophosphoric, phosphonic, and thionophosphonic acid esters of 2- hydroxyquinoxaline having the formula "Ton N/ with phosphoruscontaining ester halides having the formula (Ila) in which R, R and X are the same as defined above, and Hal is a halogen atom, including chlorine, bromine, fluorine, and iodine, and especially chlorine.

Advantageously, the particular new compounds of general formula (I) have strong arthropodicidal, i.e., insecticidal and acaricidal, properties, such as for instance an excellent activity against eating and sucking insects, as well as an outstanding activity against spider mites and ticks. The particular new compounds according to the present invention are, in this respect, superior to the known products of analogous constitution and having the same type of activity; therefore they constitute a genuine enrichment of the art.

The process for producing the particular new compounds of the present invention takes place according to the following equation:

In such equation, R, R, X and Hal have the same meanings as defined above.

The process according to the present invention is preferably carried out with the concurrent use of suitable solvents or diluents. Practically all inert organic solvents or mixtures thereof can be used for this purpose, such as optionally halogenated hydrocarbons, for example, benzine, benzene, toluene, chlorobe'nzene and xylene; others, for example, diethyl ether, dibutyl ether and dioxan; and ketones; for example, acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone. However, low boiling aliphatic alcohols, for example, methanol or ethanol, and, in particular, nitriles, for example, acetonitrile and propionitrile, as well as dimethyl formamide, have proved to be especially suitable for this purpose.

Furthermore, the reaction according to the present invention is preferably carried out in the presence of acid acceptors. Practically all customary acid-binding agents can be used for this purpose. Alkali metal alcoholates and carbonates, such as potassium and sodium methylate and ethylate, and sodium and potassium carbonate, as well as tertiary aliphatic, N-aliphatic-N-aromatic and heterocyclic amines, for example, triethylamine, dimethyl aniline and pyridine, have proved especially useful.

The reaction temperature may be varied within a fairly wide range. In general, the reaction is carried out substantially between about 20 and 120C. (or the boiling point of the reaction mixture), preferably at 40 to C.

The starting materials and the auxiliaries (acidbinding agents) are generally used in stoichiometric quantities. After the starting components have been mixed together, it is advantageous to continue heating the reaction mixture for some time (about 1 to 3 hours), possibly with stirring, in order to complete the reaction. By this method, the products of the present process are obtained in excellent yields and with a high degree of purity.

Some of the esters according to the present invention are colorless crystals with a sharp melting point; if necessary, these can easily be further purified by recrystallization from conventional solvents. In most cases, however. the compounds are colorless to yellow colored, viscous, water-insoluble oils which cannot be distilled without decomposition but which can be freed from the last volatile components and purified in this way by a so-called partial distillation, i.e. by prolonged heating at moderately elevated temperatures under reduced pressure Determination of the refractive index may serve for a more specific characterization.

As has already been mentioned above, the products of the present process are characterized by an outstanding insecticidal and acaricidal activity. At the same time, they have only a low toxicity towards warmblooded animals and a low phytotoxicity. The effect appears rapidly and is long-lasting. The compounds according to the present invention can, therefore, be used with good results in plant protection for combating noxious sucking and eating insects and Diptera and in this field, as well as in veterinary medicine, against mites (Acarina). The excellent activity of the particular new compounds against strains of spider mites which are resistant to phosphoric acid esters is to be especially emphasized.

The sucking insects contemplated herein essentially include aphids, such as the peach aphid (Myzus persicae) and the black bean aphid (Doralis fabae); coccids, such as Aspidiotus hederae, Lecanium hesperidum and Pseudococcus maritimus; Thysanoptera, such as Hercinothripa femoralis; and bugs, such as the beet bug (Piesma quadrata) and the bed bug (Cirnex leczularius); and the like.

The eating insects contemplated herein essentially include butterfly larvae, such as Plutella mac-ulipennis and Lymantria dispar; beetles, such as grain weevils (Silophilus granarius) and the Colorado beetle (Leptz'notarsa decemlineata); and also species living in the soil, such as wire worms (Agriotes sp.) and cockchafer larvae (Mololonlha melolonlha); cockroaches, such as the German cockroach (Blatella germanica); Orthoptera, such as the cricket (Gryllus domesticus); termites, such as Recticulitermes; and Hymenoptera, such as ants; and the like.

The Diptera contemplated herein mainly comprise the flies, such as the fruit fly (Drosophila melanogaster), the Mediterranean fruit fly (Ceratitis capitata) and the house fly (Musca domestics); gnats, such as the mosquito (Aedes aegypti); bluebottle flies, such as the gold fly (Luciliu sericata); and blowflies (Chrysomya chropyga); and the like.

Among the mites contemplated herein, the spider mites (Tetranychidae) are of special importance, such as the common spider mite (Tetranychus urticae) and the fruit tree spider mite (ParaIetranyc/zus pilosus); gall mites, such as the red current gall mite (Eriophyes ribis) and tarsonemides, such as Tarsonemus pallidus; and also ticks, such as Buophilus microplus and scab mites; and the like.

Advantageously, the active compounds according to the present invention are equally suitable as insecticides and acaricides in plant protection and also for 4 combating hygiene pests, for example, in homes, stables and store rooms.

Thus, the new compounds of the instant invention can be used as pesticides either alone or in admixture with solid or liquid carriers or diluent.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with dispersible carrier vehicles, such as solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granulates, etc. These are prepared in known manner, for instance by extending the active agents with dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g., surfaceactive agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents (cf. Agricultural Chemicals, March l960, pages 35-38). The following may be chiefly considered for use as carrier vehicles for this purpose: dispersible liquid diluent carriers, such as aromatic hydrocarbons (for instance, benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (for instance, chlorobenzenes), paraffins (for instance, petroleum fractions), chlorinated aliphatic hydrocarbons (for instance, methylene chloride, etc.), alcohols (for instance, ethanolamine, etc. amides (for instance, dimethyl formamide, etc. sulfoxides (for instance, dimethyl sulfoxide, etc.), ketones (for instance, acetone, etc.), and water; as well as dispersible finely divided solid carriers, such as ground natural minerals (for instance, kaolins, alumina, silica, chalk, i.e calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals (for instance, highly dispersed silicic acid, silicates, e.g., alkali silicates, etc.); whereas the following may be chiefly considered for use as carrier vehicle assistants, e.g., surface-active agents, for this purpose: emulsifying agents, such as non-ionic and anionic emulsifying agents (for instance, polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl aryl-polyglycol ethers, magnesium stearate, sodium oleate, etc.); and dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

As will be appreciated by the artisan, the active compounds according to the instant invention may be present in such formulations or compositions in the form of mixtures with one another and with other known active substances, if desired.

The substances according to the invention may be employed by themselves as the artisan will appreciate, in the form of their compositions with solid or liquid dispersible carrier vehicles or other known compatible active agents, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granulates which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.l% by weight, and preferably 05-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0000001 and 20%, preferably 0.0000l and 5%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise-mixtures of a dispersible carrier vehicle, such as l a dispersible carrier solid, or (2) a dispersible carrier liquid preferably ineluding a carrier vehicle assistant, e.g., surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.000001 and 95% by weight of the mixture.

Furthermore, the present invention contemplates methods of combating pests, especially insects and acarids, which comprise applying to at least one of (a) such pests and (b) their habitat, a pesticidally, especially insecticidally and/or acarieidally, effective amount of the particular active compound of the invention alone or together with a carrier vehicle, as noted above. The instant formulations or compositions are applied in the usual manner, for example, by spraying, atomizing, scattering, dusting, watering, sprinkling, va porizing, and fumigating, and the like. It will be realized in accordance with the present invention that the instant compounds may be used effectively not only in plant protection, but also in hygiene control, especially against insects and acarids.

The outstanding pestieidal, and especially insecticidal and acaricidal, activity of the particular new compounds of the present invention can be seen from the following Examples. I t

' EXAMPLE 1 Myzus test (contact action) Solvent: 3 parts by weight acetone Emulsifier: l part by weight alkylaryl polyglyeol ether To produce a suitable preparation of the particular active compound, 1 part by weight of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the concentrate is diluted with water to the desired final concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested with peach aphids M yzus persicae) are sprayed with the stated preparation of the given active compound until dripping wet.

After the specified period of time, the degree of destruction is determined percentagewise: 100% indicated that all the aphids are killed, whereas 0% indicates that none are killed.

The active compounds, their concentration, the evaluation time and the results obtained can be seen from the following Table l:

TABLE 1 (Plant damaging insects) Active compound Concentration Degree of of active compound destruction in after 24 hours N 9 (III) 0.01 100 0.001

S N n V) 2"'s 2 0.001 100 S N g z s 0.001 100 0.0001 95 N 0.1 100 (VII) 0.01 100 0.00l

(VIII) 0.1 0.01 100 0.001 100 N---=CH S I (OC H (IX) 2 2 5 2 0.1 100 0.0l 40 (compound known U.S. Patent Specification No. 2,758,115)

7 EXAMPLE 2 Tetranychus test common spider mites (Tetrunychus urticae) in all stages of development.

After the specified period of time, the effectiveness of the particular preparation of active compound is determined by counting the dead mites. The degree of destruction is expressed percentagewise: 100% indicates that all the spider mites are killed, whereas indicates that none are killed.

The active compounds, their concentrations, the evaluation time and the results obtained can be seen from the following Table 2:

TABLE 2 EXAMPLE 3 Plutella test Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether.

To produce a suitable preparation of the particular active compound, 1 part by weight of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the concentrate is diluted with water to the desired final concentration.

Cabbabe leaves (Brassica oleraceu) are sprayed with the preparation of the given active compound until dew moist, and are then infested with caterpillars of the diamondback moth (Plutella maculipennia).

After the specified period of time, the degree of destruction is determined percentagewise: 100% indicates that all of the caterpillars are killed, whereas 0% indicates that none are killed.

The active compounds, their concentrations, the evaluation time and the results obtained can be seen from the following Table 3.

(Plant damaging mites) Active compound Degree of Concentration of destruction active compound after 48 hours in in 'X.

i. (III') o p(oc H 0.l I00 2 5 2 0.0] N

S N o i '(oc H (IV) @E I 2 5 2 0.1 100 0.001 40 5 oc H o-i 2 5 (v) H 0.01 100 0C H ISO (v N\ 3 7 01 I00 q s 0:0l

S OC H O P\ 0 l :00 (VIII) 3 0101 R 3. (IX') N-cu -s-ptoc H 0.| 100 l 2 5 2 0.01 0 N Specification No. 2,758.| l5) TABLE 3 (Plant damaging insects) Active compound Degree of Concentration destruction of active compound after 4 days in in O-P 'oc H l I") 2 5 2 0.001 100 0.0001 30 S N 11 C H (I T 2 5 2 0.0001 100 fi oc u (V") 0.0001 100 c H 0.00001 20 N OC H (vl') 0.001 100 C H 0.0001 75 N oc H (v111" 2 5 0.001 100 0.0001 100 3 0.00001 70 P -CH -S-P 0c H 0 I 2 2 5)2 0.001 100 1 0.0001 0 (compound known from U.S. Patent Specification No. 2.75 8,1 [5) EXAMPLE 4 Boophilus test Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarly polyglycol ether.

Ten female ticks (Boophilus microplus) are placed on a small cotton pad which is subsequently immersed in thepreparation of the given active compound. After one minute, the cotton pad is removed from the solution and placed in a glass disc containing filter paper. The ticks are removed from the cotton pad and placed on dry filter paper. After the specified period of time, the degree of destruction is determined percentagewise: 100% indicates that all the ticks are killed, whereas 0% indicates that none are killed.

The active compounds, their concentrations and the results obtained can be seen from the following Table 4:

Active compound Concentration of Degree of Active Compound Destruction in after 72 hours N 111 z s z 0.5 100 0.05 25 O-P(OC H m 2 5 2 0.0025 100 I 0.0005 50 N 3 oc H 2 5 V' 0.0005 100 \C H 0.00025 65 S o i; CZHS \C H 100 0.001 (V 6 5 0.00025 55 N 1 1 OCH OCH 1.0 100 N 3/ OCH 0 c H 100 I, 0.0005 (VII N/ 3 7 0.00025 50 EXAMPLE 4 a Drosophila test Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

muiia (plant damaging insects) Active compound Concentration of Degree of active compound destruction after 72 hours 5 0 II P-S-CH X"') (C2H5m2 2 k n 0.1 o

..O-P(OC H (111) j 2 5 2 0.1 0.01 100 u Contir1ued (plum1101110 211111insects) .\\'ti\'e compound ("oncentrution of Degree of active compound destruction 'l after 72 hours oc H -i N o 3 7 o 1 100 (Vll" S oc H v1n"' -O-P 2 0.1 100 CH 0.01 100 S 1 OC H 2 5 0.1 100 0.01 100 c H 0.001 100 The following Examples are given for the purpose of EXAMPLE 6 illustrating the production process in accordance with the invention:

EXAMPLE 5 59 grams (0.4 mol) of 2-hydroxyquinoxaline are heated under reflux, together with an equimolar amount of dried, finely sieved potassium carbonate, in 350 ml. of acetonitrile for 13 minutes, while stirring, and 60 g. of 0,0-diethyl-phosphoric acid ester chloride are subsequently added dropwise to the reaction mixture at 50 to 55C.

The reaction mixture is stirred for a further 2 hours at 75C., allowed to cool, mixed with 500 ml. of benzene and the soluble components are washed out by shaking several times with water. The organic phase which results is dried over sodium sulfate and the solvent evaporated under reduced pressure finally using a so-called partial distillation at 70C. and 0.1 mm Hg.

In this way, 94 g. (83.5% of theory) of 0,0-diethylphosphoric acid-0[quinoxalyl-2)] ester are obtained in the form of a yellowish oil which cannot be distilled without decomposition and which has the refractive index n" 1.5383.

Analysis: Calculated for C, H -,N- ,O P (molecular weight 282.2):

Found: N. 10.15% P, 11.12%

3 oc H N\ 2 5 @E N 44 grams (0.3 mol) of 2-hydroxyquinoxaline are stirred with 750 ml. of dimethyl formamide and an equivalent amount of methanolic sodium methylate solution is added to this mixture, which is then concentrated under reduced pressure to a volume of 200 ml. The resultant solution is mixed dropwise at 60C. with 66 g. of phenyl-thionophosphonic acid-O-ethyl ester chloride and subsequently further stirred at to C. for two hours. Working up of the reaction mix ture as in Example 5 gives g. (86% of theory) of phenyl-thionophosphonic acid-O-ethyl-0-[quinoxalyl- (2)] ester in the form of white crystals which melt at 142C, after recrystallization from benzene/ligroin.

Analysis2' Calculated for C H, N O PS (molecular weight 330.4):

Found: P, 9.75%; S, 9.89%.

EXAMPLE 7 (IVIIIII) 15 16 with 36 g. of triethylamine. 66 grams of 0,0-diethy1- The compound, ethyl-thionophosphonic acid-- thionophosphoric acid ester chloride are added dropethyl-O-[quinoxalyl-(2)] ester, has the formula wise to this mixture, which is subsequently stirred for a further 2 hours, while boiling under reflux. Working S up of the reaction mixture is carried out in the manner described in Example 5. 85 grams (81.5% of theory) of N -P-0-C H 0,0-diethyl-thionophosphoric acid-0-[quinoxalyl-(2)] (I I ester are obtained in the form ofa darkyellow oil which c 11 has the refractive indes n 1.5624. and which decomposes when distilled. M.p. 35 36C (from ligroin) EXAMPLE 9 In the same manner, using corresponding molar amounts of Z-hydroxyquinoxaline and each of the fol- Analysis: Calculatcd for C H N Q Ps (molccular weight 298.3 i t ti mat i l s ti l P, 10.38%; S. 10.75% 3 5'- v Fmmd P 10 S 10 7 a. 0,0-d1-n-propy1-phosphor1c acid ester chloride;

b. 0,0-di-tert.-butyl-phosphoric acid ester chloride; c. 0,0-diisopropyl-thionophosphoric acid ester chlo- EXAMPLE 8 id The following Compounds of the general formula. d. 00-di-sec.-butyl-thionophosphoric acid ester chlon e; 5 e. methyl-phosphonic acid-0-tert,-buty1 ester ch10- N OR ridea I 1 f. isobutyl-phosphonic acid-O-n-propyl ester chloride;

N (Ia) g. n-propy1-thionophosphonic acid-O-n-butyl ester chloride; are obtained in a manner analogous to that described h. sec.-butyl-thionphosphonic acid-O-isopropyl ester in Examples 5 to 7. chloride;

Yield Empirical Molecular Analysis in of Physical R R formula weight calc. found theory constants n Ch, OCl-L, C H N O PS 270.2 P 11.46 P 11.73 71 15573 (X') S 11.87 S 12.60 i-C H, OCH, C H, N O;,PS 298.1 P 10.38 P 9.56 82 1.5603 (Vll"") S 10.70 S 9.99 c 11 c1-1 c,,1-1,,N o,1 s 268.2 P 11.60 P 13.10 69 1.5768 (X1) S 11.90 S 13.40 c 11,, c 11,, c, H,,.,N o,1 s 282.3 P 10.90 P 11.7 78 1.5802 (V""' S 11.36 S 11.25

The compound 0,0-dimethyl-thionophosphoric i. phenyl-phosphonic acid-O-methyl ester chloride; acid-0-[quinoxaly1-(2)] ester, has the formula j. phenyl-phosphonic acid-O-tert.-buty1 ester chloride; a k. phenyl-thionophosphonic acid -0-isopropy1 ester ..P Q-CH3 chloride;

1. phen l-thiono hos honic acid-O-n-but lester chloo y P P Y N (XH) ride;

the particular phosphoric, thionophosphoric, phos- The compound, y p py phonic, and thionophosphomc acid esters respective y are formed.

thionophosphorlc ac1d-0-[qu1noxa1yl-(2)] ester, has

the formula a. 0,0-di-n-propyl-phosphoric acid-O-[quinoxalyl- (2)] ester; b. 0,0-di-tert.-butyl-phosphoric acid-O-[quinoxalyl- (2)] ester;

0- T CH3 C c. 0,0-di-iso-propyl-thionophosphor1c ac1d-O- O-CH 3 [quinoxalyl-(2)] ester;

\ W d. 0,0-di-sec,-butyl-thionophosphoric acid-O- [quinoxa1yl-(2)] ester; The compound, methyl-thionophosphoric acid-O- e. methyl-phosphonic acid-0-tert.-buty1-O- ethy1-O-[quinoxa1yl-(2)] ester. has the formula [quinoxa1yl-(2)] ester;

f. iso-butyl-phosphonic acid-O-n-propyl-O- [quinoxa1yl-(2)] ester; g. n-propyl-thionophosphonic acid-O-n-butyl-O- S N o c H T K 2 5 [quinoxalyl-(2)] ester; CH h. sec.-butyl-thionophosphonic acid-O-iso-propyl-O- [quinoxaly1-(2)] ester;

i. phenyl-phosphonic acid--methyl'0-[quinoxalyl- (2)] ester;

j'. phenyl-phosphonic [quinoxalyl-(2)] ester;

k. phenyl-thionophosphonic [quinoxalyl-(2)] ester;

phenyl-thionophosphonic [quinoxalyl-(2)] ester.

It will be appreciated, in accordance with the present invention, that in the foregoing formulae:

R represents alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, and particularly alkyl having I to 3 carbon atoms, i.e., methyl, ethyl, npropyl, and iso-propyl;

R represents alkyl having 1 to 4 carbon atoms, such as methyl to tert.-butyl, inclusive. i.e., the radicals specifically mentioned under R, and particularly alkyl having 1 to 3 carbon atoms, i.e., methyl, ethyl, n-propyl, and isopropyl; lower alkoxy, such as methoxy, ethoxy, n-propoxy, iso-propoxy, nbutoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, and the like, and particularly alkoxy having 1 to 3 carbon atoms, including methoxy, ethoxy, n-propoxy and iso-propoxy; or phenyl; and

X represents oxygen or sulfur, preferably sulfur.

in accordance with a preferred feature of the invention, R is C -C alkyl; R is C C alkyl, C,C alkoxy, or phenyl; and X is oxygen or sulfur, preferably sulfur.

Thus, the preferred subgeneric aspects of the present invention contemplate:

0,0-di(C,-C, alkyl) phosphoric acid-O-[quinoxalyl- (2)] ester having the formula acid-0-tert,-butyl-0- acid-O-isopropyl-O- l. acid-O-n-butyl-O- O N n O,0-di(C C alkyl-thionophosphoric [quinoxalyl-(2)] ester having the formula o-(c -c alkyl) o-(c -c, alkyl) (13) acid-O- o-(c -c alkyl) C -C alkyl-phosphonic acid-0-(C -C [quinoxalyl-(2)] ester having the formula alkyl)0- j-O-P\-O(C -C alkyl) ,-c lkyl) Phenyl-phosphonic acid-O-(C C, alkyl )-0- [quinoxalyl-(2)] ester having the formula N jo-r-oc -c, alkyl) Phenyl-thionophosphonic acid-0-(C -C [quinoxalyl-(2)] ester having the formula All of the foregoing compounds contemplated by the present invention possess the desired pesticidal, and especially insecticidal and acaricidal, activity, whereby the'combating of pests, such as arthropods, may be attained effectively.

It will be appreciated that as contemplated herein, the terms arthropod, arthropodicidal and arthropodicide may be defined as encompassing specifically both insects and acarids within the contemplation of their meaning, for convenience in determining the collective aspects of utility herein. Thus, the insects and acarids may be considered herein collectively as arthropods to be combated collectively in accordance with the invention, and accordingly the insecticidal and/or acaricidal activity may be termed arthropodicidal activity; and the concomitant combative or effective amount used in accordance with the invention will be an arthropodicidally effective amount which in essence means an insecticidally or acaricidally effective amount of the active compound for the desired purposes.

It will be appreciated that the instant specification alkyl)-0- and examples are set forth by way of illustration andnot limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention which is to be limited only by the scope of the appended claims.

What is claimed is:

1. An insecticidal and acaricidal composition which comprises a dispersible carrier vehicle and an insecticidally and acaricidally effective amount of between about 0000001 and by weight of the composition of a phosphorus-containing ester of 2-hydroxyquinoxaline having the formula X N u /O'R (1 7 in which R is alkyl having 1 to 4 carbon atoms, R is a member selected from the group consisting of alkyl having 1 to 4 carbon atoms, lower alkoxy having 1 to 4 carbon atoms and phenyl, and X is selected from the group consisting of oxygen and sulfur.

2. The composition according to claim 1 wherein said phosphorus-containing ester is 0,0-diethyl-phosphoric acid-0-[quinoxalyl-(2)] ester, 0,0-diethyl-thionophosphoric acid-O-[quinoxalyl- (2)] ester, ethyl-thionophosphonic acid-O-ethyl-O-[quinoxalyl- (2)] ester, phenyl-thionophosphonic [quinoxalyl-(2)] ester, 0,0-dimethyl-thionophosphoric (2)] ester, O-methyl-O-iso-propyl-thionophosphoric [quinoxalyl-(2)] ester or methyl-thionophosphonic [quinoxalyl-(2)] ester.

acid-O-ethyl-O- acid-O-[quinoxalylacid-0- acid-O-ethyl-O- 3. A method of combating pests selected from the group consisting of insects and acarids which comprises applying to at least one of (a) such pests and (b) their habitat, an insecticidally and acaricidally effective amount of a phosphorus-containing ester of 2- hydroxyquinoxaline having the formula in which R is alkyl having 1 to 4 carbon atoms, R is a member selected from the group consisting of alkyl having 1 to 4 carbon atoms, lower alkoxy having 1 to 4 carbon atoms, and phenyl, and X is selected from the group consisting of oxygen and sulfur.

4. The method according to claim 3 wherein said ester is 0,0-diethyl-phosphoric acid--[quinoxalyl-(2)] ester.

5. The method according to claim 3 wherein said ester is 0,0-diethyl-thionophosphoric acid-O- [quinoxalyl-(2)] ester.

wherein R and R are alkoxy of up to 4 carbon atoms.

UNITED STATES PATENT OFFICE CE RTI FICATE (191? (10B R EC'lIrff) N I PATENTNO. 1 3,880,997

. DATED April 29, 1975 5 TOMS) KARL-JULIUS SCHMIDT et al It is certified that error appears in the above-machined parent and that said Letters Potent are hereby corrected as shown below:

Col. 1, line 34, correct spelling of "acarids.

Col. 7 line 13, correct spelling of "vulgaris".

Col. 7, Table 2, Compound (\ZII') cancel "q" at bottom of structural formula.

Col. 9, V line 56, correct spelling of "alkylaryl".

0 Col. 11, Table 4, 5th Compound, cancel "I" and substitute Col. 11, Table 4a, Compound (IX' correct formula to read as I follows: S O H l H (C H O) P-SCH -1 r C01. 15, line 61, cancel "-thionophosphoric" and substitute -thionophosphonic o I En'gncd and Scaledmhis eleventh Of November 75 [SEAL] Arrest: G

RUTH (r MASON C. MA'RSHALL DANN illcsrmg lfrre'r' unmrmrmrw' n! Pure/11x um] lrrrrlr'mrrrkr 

1. AN INSECTICIDAL AND ACARICIDAL COMPOSITION WHICH COMPRISES A DISPERSIBLE CARRIER VEHICLE AND AN INSECTICIDALLY AND ACARCIDALLY EFFECTIVE AMOUNT OF BETWEEN ABOUT 0.000001 AND 95% BY WEIGHT OF THE COMPOSITION OF A PHOSPHORUS-CONTAINING ESTER OF 2-HYDROXY-QUINOXALINE HAVING THE FORMULA
 2. The composition according to claim 1 wherein said phosphorus-containing ester is 0,0-diethyl-phosphoric acid-0-(quinoxalyl-(2)) ester, 0,0-diethyl-thionophosphoric acid-0-(quinoxalyl-(2)) ester, ethyl-thionophosphonic acid-0-ethyl-0-(quinoxalyl-(2)) ester, phenyl-thionophosphonic acid-0-ethyl-0-(quinoxalyl-(2)) ester, 0,0-dimethyl-thionophosphoric acid-0-(quinoxalyl-(2)) ester, 0-methyl-0-iso-propyl-thionophosphoric acid-0-(quinoxalyl-(2)) ester or methyl-thionophosphonic acid-0-ethyl-0-(quinoxalyl-(2)) ester.
 3. A method of combating pests selected from the group consisting of insects and acarids which comprises applying to at least one of (a) such pests and (b) their habitat, an insecticidally and acaricidally effective amount of a phosphorus-containing ester of 2-hydroxyquinoxaline having the formula
 4. The method according to claim 3 wherein said ester is 0,0-diethyl-phosphoric acid-0-(quinoxalyl-(2)) ester.
 5. The method according to claim 3 wherein said ester is 0,0-diethyl-thionophosphoric acid-0-(quinoxalyl-(2)) ester.
 6. The method according to claim 3 wherein said ester is ethyl-thionophosphonic acid-0-ethyl-0-(quinoxalyl-(2)) ester.
 7. The method according to claim 3 wherein said ester is phenyl-thionophosphonic acid-0-ethyl-0-(quinoxalyl-(2)) ester.
 8. The method according to claim 3 wherein said ester is 0,0-dimethyl-thionophosphoric acid-0-(quinoxalyl-(2)) ester.
 9. The method according to claim 3 wherein said water is 0-methyl-0-iso-propyl-thionophosphoric acid-0-(quinoxalyl-(2)) ester.
 10. The method according to claim 3 wherein said ester is methyl-thionophosphonic acid-0-ethyl-0-(quinoxalyl-(2)) ester.
 11. The method according to claim 3 wherein such pests are phosphoric acid ester-resistant mites and said phosphoruscontaining ester has the formula 